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Green synthesis of 3D SnO2/graphene aerogels and


their application in lithium-ion batteries
Cite this: RSC Adv., 2015, 5, 39746
a

Chen Gong, Yongquan Zhang, Mingguang Yao, Yingjin Wei, Quanjun Li, Bo Liu,
Ran Liu,a Zhen Yao,a Tian Cui,a Bo Zoua and Bingbing Liu*a

Three-dimensional (3D) tin oxide/graphene aerogels (SnO2/GAs) were constructed by a simple, facile and
environmentally friendly process. The small-sized SnO2 nanoparticles (6 nm) are encapsulated within
graphene-based aerogels with interconnected 3D networks for the SnO2/GAs nanocomposite. When

Received 31st March 2015


Accepted 17th April 2015
DOI: 10.1039/c5ra05711f
www.rsc.org/advances

used as an anode material in lithium ion batteries, it delivers a high reversible capacity that is close to the
theoretical capacities of SnO2 and graphene after 50 cycles. TEM observations of the samples before and
after 50 cycles illustrate that the structures of the graphene network and SnO2 NPs are preserved, which
explains well the good cyclic stability of the electrode. The excellent electrochemical performance of the
nanocomposites can be explained by their unique 3D porous architecture and the combination of the
advantages of both SnO2 and graphene in Li ion storage and transport.

Introduction
As one of the most popular electrochemical energy storage
devices, rechargeable lithium-ion batteries (LIBs) have been
found to be a great success as power sources in portable electronics for their excellent characteristics such as high energy
density, light weight, environmental benignity and no memory
eect.14
Graphite is the
widely used
material for
commercial
LIBs, but its limited specic capacity (372 mA h g 1 in theory)
cannot satisfy the increasing demand for batteries with higher
energy density.5,6 Up to now, various advanced anode materials
have been studied to replace graphite. Among them, SnO2 has
been proposed as one of the most promising anode candidates
for next-generation lithium ion batteries, owing to its high
theoretical capacity (782 mA h g 1) and low discharge potential
(<1.5 V).79 However, the practical use of SnO2 is greatly
hampered by the poor cycling performance arising from its low
electronic conductivity, severe aggregation, and huge volume
changes upon extended Li insertion/extraction.10,11 To solve
these problems, various nanostructured SnO2 and SnO2
composites have been proposed with the aim of stabilizing the
active electrode material by minimize the volume change
during cycling.1226 Up to now, reducing the size of SnO2 to the
nanometer range and incorporating electrochemically active/
inactive matrix have been widely applied for improving the
cycling stability of SnO2-based anodes.1226 The fabrication of
SnO2/carbon (e.g., graphene, amorphous carbon, carbon

State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012,


People's Republic of China. E-mail: liubb@jlu.edu.cn
a

Key Laboratory of Physics and Technology for Advanced Batteries, College of Physics,
Jilin University, Changchun 130012, People's Republic of China
b

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3974639751

nanotubes, etc.) nanocomposites has been extensively investigated, because the carbon may both accommodate the volume
variation and provide an electrical conduction pathway.1626
According to recent studies, graphene is regarded as a superior carbon matrix to create SnO2/graphene hybrids due to its
excellent electrical conductivity, high carrier mobility and large
surface area.27 Several SnO2/graphene hybrids with various
assemblies such as directly decorated SnO2/graphene, SnO2/
C-graphene, and sandwich-like graphene-supported hybrids
have been developed.1926 Although improved electrochemical
performances have been achieved in these hybrid anodes, the
performance is still limited by the following obstacles. (1) The
graphene sheets tend to irreversible aggregation or restacking
due to the strong van der Waals interactions among individual
graphene sheets, resulting in a seriously reduced active surface
28

area and carrier mobility. The conventional direct hightemperature calcination could easily result in severe agglomeration of the graphene sheets; (2) in some SnO2/graphene
hybrids, the exposed active SnO2 nanostructures, which
are simply decorated on the surface of graphene sheets, are
hard to avoid volume expansion and aggregation during the
cycle processes due to the non-intimate contact between
graphene nanosheets
and active materials;29 (3) the shape, size and dispersion
uniformity of SnO2 nanoparticles which signicantly inuence
the electrochemical performance of SnO2/graphene composites
are still dicult to control. Therefore, it is urgent to develop
new SnO2/graphene hybrids with unique structures to
overcome these
obstacles for higher electrochemical
performances.
Three-dimensional (3D) macroscopic frameworks of graphene sheets could eectively prevent restacking of graphene,
provide large specic surface area, porous structure, and fast
electron conductivity due to the continuous graphene

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backbone, which might be used as ideal support for the nanoparticles and thus promising for higher electrochemical
performances.3033 Moreover, in such geometric architectures,
nanoparticles could conned within graphene layers which
could enhance their interface interaction and mitigate the
volume expansion and aggregation of nanoparticles, promoting
the Li+ storage property.3339 For example, Chen et al. pioneered
the capture of prepared Fe3O4 into 3D graphene network which
delivered a high capacity of 730 mA h g 1 even at a current
density of 1600 mA h g 1.33 Besides, 3D Fe2O3/GAs,34 TiO2/GAs,35
CoO/GAs,36 and Co3O4/GAs37 also demonstrated the eectiveness of macroscopic 3D architectures to the nal lithium
storage properties. These ndings motivated our idea of
synthesize 3D SnO2/GAs as anode materials in lithium ion
batteries. During our research process, Wang et al. reported
their work on 3D N-doped SnO2/GAs.38 They successfully constructed SnO2/GAs via a solvothermal process (high temperature) using DMF as reducing agent, and they found that the as
prepared material exhibits superior rate capability. It is well
known that, exploring facile and environmental friendly
synthetic methods for function materials is a signicant issue
for practical industrial applications. It thus inspired us to nd a
simple and environmental friendly synthetic process for 3D
SnO2/GAs. From the literature, 3D GAs can be successfully
constructed using nontoxic sodium ascorbate as reducing
agent.39 We believe that it is possible to nd a promising ecofriendly approach to synthesize SnO2/GAs.
Herein, we report a simple, facile and environmental friendly
method for the preparation of 3D SnO2/graphene aerogels
(SnO2/GAs). The 3D SnO2/GAs are synthesized by a two step
procedure, for which SnO2 NPs were rstly prepared and then
directly decorated on and between graphene sheets under mild
conditions (95
C) with nontoxic sodium erythorbate as
reducing agent. This allows us to control the size and shape of
SnO2 NPs
which would inuence the electrochemical performance. The
mild synthesis condition could further prevent agglomeration
of the
graphene sheets. Therefore, such
prepared 3D
SnO2/GAs could overcome the disadvantages of SnO2/graphene
hybrids, and
expect to exhibit
better
electrochemical
performances for LIBs. Moreover, this synthetic method for
SnO2/GAs could extend to other 3D graphene hybrids.

Experimental
Materials preparation
Synthesis of SnO2 nanoparticles (SnO2 NPs). Typically, lysteine (Lys, C6H14N2O2, >99% purity, 10 mmol) was dissolved in
20 mL of deionized water to form solution A. SnCl4$5H2O
(Analytic reagent, AR, 2 mmol) was dissolved in 20 mL of
deionized water to form solution B. And then solution A was
added into solution B with stirring for 12 h at room temperature. Aer that, the mixture was sealed into a 50 mL Teonlined autoclave, heated and maintained at 180 C for 10 h.
Aer cooled down to room temperature naturally, the products
were
collected and washed with deionized water and then absolute
alcohol, and then dried at 60 C for 4 h.

RSC Advances
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Synthesis of 3D graphene aerogels (GAs). Graphene oxide


was synthesized from natural graphite by a modied Hummer's
method.40 60 mg of GO was dissolved in 60 mL of distilled water
with ultrasonic treatment for 4 h to form a suspension. Then,
120 mg sodium erythorbate was added into the suspension
under magnetic stirring. The mixture was heated at 95 C for 3
h under atmosphere pressure without stirring to form
graphene hydrogels. The reduced graphite oxide hydrogels
were cleaned by immersing in water for many times. The
pure graphene hydrogels obtained were freeze-dried to prepare
3D graphene aerogels (GAs).
Synthesis
of SnO2/GAs. Composites were obtained by
following the same procedure of GAs. In brief, 120 mg SnO2
were dispersed to 60 mL 1 mg mL 1 GO suspension by ultrasonication. 120 mg sodium erythorbate was added into the
suspension under magnetic stirring, and
SnO2/graphene
hydrogels were synthesized at 95 C for 3 h under atmosphere
pressure without stirring. The SnO2/graphene hydrogels were
immersed in water to remove impurities. Then the hydrogels
were freeze-dried to get SnO2/GAs.
Electrochemical measurements
Electrochemical experiments were carried out using 2032-type
coin cells. A metallic Li foil was used as the anode electrode.
The cathode electrode was composed of 70 wt% active material, 15 wt% carbon black conductive additive, and 15 wt%
poly(vinylidene
uoride) binder dissolved in N-methyl-2pyrrolidone. The cathode slurry was coated on Cu foil. Each
electrode was 8 8 mm 2 in size with a SnO2/GAs mass loading
of 3 mg cm 2. The cathode and anode electrodes were
separated by the Celgard 2320 membrane. The electrolyte used
1
was 1 mol L
lithium hexauorophosphate dissolved in
ethylene carbonate (EC) and dimethyl carbonate (DMC)
[EC : DMC 1 : 1 (w/w) ratio]. Galvonostatic chargedischarge
cycling was performed on a Land-2100 battery tester (Wuhan,
China). EIS was performed on a Bio-Logic VSP multichannel
potentiostaticgalvanostatic system (France). The impedance
data were recorded by applying an alternating-current voltage
of 5 mV in the frequency range from 1 MHz to 5 mHz.

Results and discussion


The 3D SnO2/GAs were fabricated by a simple, fast and environmental friendly method described above. SnO2 nanoparticles (see Fig. 1a), with an average diameter of 6 nm,
uniformly disperse on the surface of GO when they were mixed
together (see Fig. 1b). Noteworthy, even aer a long time of
sonication, SnO2 NPs still stably anchored on GO, demonstrating the strong interaction between them. High-resolution
TEM (Fig. 1c and d) revealed that well crystalline SnO2 NPs
were encapsulated by graphene sheets. Fig. 2a and b show the
SEM images of SnO2/GAs. The images revealed that an interconnected, porous 3D graphene framework with continuous
macropores is formed in the composite. Graphene sheets
decorated with SnO2 NPs acted as a building block and selfassembled into a 3D interconnected network, driven by pp

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stacking interactions due to the decrease of oxygenated groups


on graphene. The pore size of the network is distributed in the
range of submicrometer to several micrometers and the walls
consist of several layers of stacked graphene sheets. Apart from
the decoration of SnO2 NPs on both sides of the graphene
sheets, a large part of the NPs are encapsulated within the
graphene layers, suggesting ecient assembly between
the
SnO2 NPs and the graphene sheets. Such a geometric connement of NPs within graphene layers has been reported in some
other metal oxides, which is supposed to enhance their interface contact and to suppress the dissolution and agglomeration
of NPs, thereby promoting the electrochemical activity and
stability of the hybrids.41,42
Fig. 3a shows XRD patterns of as-prepared SnO2/GAs nanocomposite and graphene aerogels. All diracted peaks from
SnO2 and can be well indexed by a tetragonal phase with space
group P42/mnm (JCPDS Card no: 8 8-0287). The broad
diracted peaks of the SnO2/GAs composite should be caused
by the nano- sized eect of the formed SnO2 nanoparticles. A
weak and broad diracted peak in the XRD pattern of GAs
can also be seen in Fig. 3a. The presence of this peak indicates
that graphene sheets
contrast, no visible diracted peak from stacked
graphene sheets can be identied in the pattern of SnO2/GAs,
indicating
that SnO2 NPs were eciently deposited on the
graphene surface, suppressing the stacking of graphene layers.
Raman spectroscopy is a convenient and nonvolatile technique for the characterization of graphitic materials. Fig. 3b
shows the recorded Raman spectra of GAs and SnO2/GAs. The D
band and G band in both spectra are related to the defects/
disorder in the graphitic layers and stretching vibration of sp2
C in a graphene layer, respectively.43 The intensity ratio ID/IG of

stacked into multilayers and aggregated to some extend. In

Fig. 2

SnO2/GAs ( 1.26) is higher than that of the GAs ( 0.92). The


2

result suggests a decrease of the sp C upon reduction of the


exfoliated GO.43,44
XPS was used to characterize the chemical information of the
samples. Fig. 3c shows the high-resolution spectra of C1s in GAs
and SnO2/GAs samples. The C1s XPS spectrum of the GAs
sample can be deconvoluted into four peaks with binding
energies of 284.4 eV for CC, 286.1 eV for CO (including COH,
COC), 288.4 eV for C]O, and 291.1 eV which is identied as a
shake-up satellite due to pp* transitions.45,46 In comparison

(a) XRD patterns of SnO2/GAs and GAs; (b) Raman spectra of


GAs and SnO2/GAs; (c) XPS C1s spectra of SnO2/GAs and GAs; (d) XPs
Sn 3d spectra of SnO2/GAs and SnO2.
Fig. 3

Fig. 1 (a) TEM image of SnO2 NPs; (b) TEM image of SnO2/GAs; (c and

d) HRTEM images of SnO2/GAs.

SEM images of SnO2/GAs.

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with GAs, the peak position of CO of SnO2/GAs sample


downshied to 285.8 eV. Such a shi suggested the decrease
of COC (epoxide groups) in CO groups. The XPS spectra of
Sn
3d from the SnO2 and SnO2/GAs samples are shown in Fig. 3d.
The symmetric peaks centered at 487.0 and 495.5 eV are
assigned to Sn 3d5/2 and Sn 3d3/2, respectively, which are characteristic for Sn4+ in the SnO2 NPs.46 We noted that the peaks of
Sn 3d5/2 and Sn 3d3/2 in SnO2/GAs upshi to 487.4 and 495.8
eV, which are higher than those of as-prepared SnO2 NPs.
Such
dierences in binding energy probably indicate the presence
of charge transfer between SnO2 NPs and graphene sheets.
The porous nature of SnO2/GAs was demonstrated by BET
measurement (Fig. 4). The specic surface area of SnO2/GAs
2
1
reached up to 539 m g . This result highlighted that the
building up of 3D frameworks was an eective way to achieve
a high surface area for hybrid materials. BJH calculations
3
1
dis- closed the pore volume was 0.265 cm g with an average
pore
diameter of 3.5 nm (the inset in Fig. 4). The high porosity can
provide not only more surface reaction sites but also
sucient buer space to alleviate the volume expansion of
SnO2 during Li insertion/extraction and is therefore in favor
of the electro- chemical properties.
The electrochemical performance of SnO2/GAs was evaluated
by the assembly of lithium half-cells with metallic lithium as the
counter electrode. Fig. 5a shows the typical rst three galvanostatic dischargecharge curves at current density of 50 mA g 1
in the potential range of 0.053.0 V vs. Li+/Li. The initial
discharge and charge capacity of SnO2/GAs electrode are 1996
1
and 1036 mA h g , respectively, giving a coulombic eciency
of
52%. The relatively low initial coulombic eciency for the
rst
cycle was mainly due to the irreversible amorphous lithium
oxide and the formation of a solid electrolyte interface (SEI)
layer over electrode. For the second cycle, the discharge and
1
charge capacities were 1090 and 1012 mA h g , respectively,
and the coulombic eciency increased to 94%.
For comparison, the cycling performance of SnO2/GAs, GAs
1
and SnO2 measured at a current density of 50 mA g are shown

Fig. 4

Nitrogen adsorption and desorption isotherms of SnO2/GAs.

in Fig. 5b. For the bare SnO2 NPs electrode, there was a rapid

(a) The rst three galvanostatic dischargecharge curves at a


1
current density of 50 mA g ; (b) the cycling performance of SnO2/
GAs, GAs and SnO2 measured at a current density of 50 mA g
1
.
Fig. 5

decrease of capacity due to the severe pulverization. Aer 50


cycles, the charge capacity was only 207 mA h g 1, which was
about 23% retention of the initial reversible capacity. The GAs
electrode displays
higher electrochemical performance,
1
showing a capacity of 542 mA h g aer 50 cycles and about
55% retention of the initial reversible capacity. This result is
obviously higher than the graphene electrode reported in
previous literatures. For instance, the charge capacity of gra1

phene electrode was only about 300 mA h g


aer tens
cycles, which is close to that of graphite. The lower cycling
perfor- mance should be caused
by the stacking and
aggregation of graphene layers,
which
decreases the
accommodation of
lithium ions. In our case, higher cycling performance of GAs is
due to its unique 3D network architectures which prevents the
agglomeration of the graphene sheets, as well as provides
abundant reactive sites and fast electron transport channels in a
3D pathway. In comparison to bare SnO2 NPs and GAs, the
charge capacity and cycling performance of SnO2/GAs
composite electrode is enhanced signicantly. The SnO2/GAs
composite shows a reversible discharge capacity of 760 mA h
1
1
g aer 50 cycles, 73% of the initial capacity (1036 mA h g ),
exhibiting a high stability in the chargedischarge process. This
reversible discharge capacity is close to the theoretical capacities of SnO2 (782 mA h g 1)7 and graphene (744 mA h g 1),47
indicating the superior advantage for electrochemical performance when both materials are hybrid to form SnO2/GAs
composite. As mentioned in previous literatures,10,11 the main
reason for the poor cyclic life of SnO2 electrodes is the huge
volume expansion produced by the alloying reaction of Li and
Sn, leading to the pulverization and subsequent electrical
disconnection of the electrodes. In our case of using SnO2/GAs
composite, both the higher mechanical strength of our 3D GAs
compared to the reported graphene materials and the strong
interaction between SnO2 NPs and graphene sheets eectively
suppress the volume change and cracking of the composite
electrode, resulting in an enhanced cycling performance. On
the other hand, the unique 3D network architectures together
with the good separation eect from SnO2 NPs prevent
agglomeration of the graphene and the stacking of graphene
layers (evidenced by XRD results), which preserve the intrinsic
capacity performance of graphene sheets. The combination of
the advantages of both SnO2 NPs and GAs thus achieves high
capacity and excellent cycling performance in their composites.

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(a) The 10th dischargecharge curves of SnO2 NPs and (b) of


SnO2/GAs
at
dierent
current
densities.
Fig. 6

Multiple-current galvanostatical tests were carried out to


investigate the high rate performance SnO2/GAs and SnO2 NPs.
Fig. 6 shows the 10th dischargecharge curves at dierent
current densities. It can be seen that the specic capacities of
1
the SnO2 NPs obviously decreased from 822 mA h g at 25 mA
1
1
1
g to 19 mA h g at 1000 mA g , while the specic capacities
of the SnO2/GAs show a signicantly higher stability as current
densities increase, leading to 929, 819, 730, 668, 582, 502, 424,
1
and 361 mA h g at 25, 50, 100, 200, 400, 600, 800 and 1000 mA
1
g , respectively. All these values from the measurements with
current densities below 1000 mA g 1 are higher than the theoretical capacity of the commonly used graphite anode material
(372 mA h g 1). The improved rate capability of SnO2/GAs
should also be related to its unique 3D network structure. The
3D conductive network increases the electronic conductivity of
the nanocomposite and facilitates the liquid electrolyte

diusion into the materials. Moreover, the nano-sized SnO2


particles can shorten the path length for electronic and Li+
transport, which also favors the high rate capability.
The structural stability of the samples aer electrochemical
measurements has been further examined by TEM. Fig. 7 shows
TEM and HRTEM images of bare SnO2 NPs and SnO2/GAs
samples aer 50 cycles at a current density of 200 mA g 1. For
bare SnO2 NPs electrode aer the charge and discharge cycling,
TEM observation shows that NPs tend to form agglomeration
(Fig. 7a) and the HRTEM image (Fig. 7b) clearly shows the loss
of crystallinity. For SnO2/GNs electrode, it is clearly seen that
the SnO2 NPs are still highly dispersed aer 50 cycles (Fig.
7c),
due to the support of the stable graphene network. Furthermore, the HRTEM image (Fig. 7d) indicated that the SnO2 NPs
still preserve crystalline structure, which can be well indexed by
the starting rutile phase. The results indicate that the charge/
discharge reactions between SnO2 and Li are reversible in the
SnO2/GAs nanocomposite. As shown in Fig. 7d, a uniform solid
electrolyte interface (SEI) layer was formed and fully covered a
SnO2 nanoparticle aer Li-ion battery measurement. Although
the formation of the SEI layer might cause partial loss of the
irreversible capacity, the SEI layer favors to maintain the robust
electrode structure by preventing the aggregation and pulverization of SnO2 NPs in the cycling process.

Conclusions
We have successfully prepared SnO2/GAs nanocomposites via a
simple, facile and environmental friendly process, for which
ultra-small SnO2 nanocrystals with a size of 6 nm are well
dispersed in the 3D graphene networks. Such unique 3D
network structure eectively prevents the agglomeration of
graphene sheets and provides open channels for lithium-ion
transport and storage. On the other hand, the 3D network
exhibit excellent structural stability and suppress the pulverization of SnO2 nanoparticles during Li ion insertion/extraction.
As a result, the reversible capacity of SnO2/GAs aer 50 cycles
still remains 760 mA h g 1, which is close to the theoretical
1
1
capacities of SnO2 (782 mA h g ) and graphene (744 mA h g ).
TEM observations on the samples before and aer 50 cycles at
a current density of 200 mA g 1 illustrates that the structures
of
the graphene network and SnO2 NPs are preserved, which well
explains the good cyclic stability of the electrode. We believe
that this simple, fast and environmental friendly synthetic route
can be further extended to produce other 3D graphene
composites, for various applications in lithium-ion batteries,
catalysts, sensors, and so on.

Acknowledgements
TEM image (a) and HRTEM image (b) of pure SnO2 NPs after 50
1
cycles at a current density of 200 mA g ; TEM image (c) and HRTEM
image (d) of SnO2/GAs after 50 cycles at a current density of 200 mA
g 1. The d-spacing of 0.33 nm corresponds to the (110) plane of a rutile
phase.
Fig. 7

This journal is The Royal


Society
of Chemistry
397503975039750
| RSC
Adv., 2015,
2015
5,
3974639751

This work was supported nancially by the National Basic


Research Program of China (2011CB808200), NSFC (51025206,
51320105007, 51032001, 11104105, 11374120), the Cheung
Kong Scholars Programme of China and 973 Program (no.
2015CB251103), and Open Project of State Key Laboratory of
Superhard Materials (Jilin University) (no. 201404, no. 201406).

RSC
Adv.,Royal
2015, Society
5, 3974639751
|
This journal is
The
of Chemistry
397503975039750
2015

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